Patent GB-823172-A (GB)
Title: Method of producing alkyl chlorides and polymeric zirconium compounds containing chloride and alkoxy groups
IPC: C08G79/00
Filed: 1957-09-23
Abstract: Zirconium dioxide may be prepared by steam hydrolysis at 300-500 DEG C. and calcination at temperatures of up to 1000 DEG  C. of polymeric zirconium compounds of the following average formula <FORM:0823172/III/1> where R is an alkyl group, x is between 0 and 2.5, and y is between 0 and 1.5, and which may contain a few hydroxyl groups if water was present in the reaction medium; such polymers are prepared either (a) by reacting ZrCl4 with aliphatic ethers at elevated temperatures, or (b) by thermally decomposing the addition compounds of ZrCl4 and aliphatic ethers (see Group IV (a)).ALSO:Polymeric zirconium compounds of the following average formula ZrO2- 1/2 (x+y)Clx(OR)y where R is an alkyl group, x is between 0 and 2.5, and y is between 0 and 1.5, and which may contain a few hydroxyl groups if water is present in the reaction medium, are prepared either (a) by reacting ZrCl4 in the aliphatic ethers at elevated temperatures, or (b) by thermally decomposing the addition compounds of ZrCl4 and aliphatic ethers, alkyl chlorides being produced as a by-product.  The preferred form of reaction (a) is to react the aliphatic ether in gas or vapour form with ZrCl4 at 150-300 DEG  C.  The preferred form of reaction (b) takes place at 120-400 DEG  C.; if the temperature is about 150 DEG  C. and the duration of the reaction is long (e.g. 35-90 hours), the products are water-soluble with high values for x and y: if the temperature is about 250 DEG  C., the products are water-insoluble, with low values of x and y.  Pressures may be normal or elevated, higher pressures favouring the production of alkyl chlorides.  The polymers may be converted into pure ZrO2 by hydrolysing with steam at 300-500 DEG  C. and calcining at temperatures up to 1000 DEG  C.  In the examples the ether used is dimethyl ether, so that R is methyl and the alkyl chloride produced is methyl chloride; values of x and y are given.ALSO:Polymeric zirconium compounds of the following average formula <FORM:0823172/IV (a)/1> where R is alkyl group, #c is between 0 and 2.5, and y is between 0 and 1.5, and which may contain a few hydroxyl groups if water is present in the reaction medium, are prepared either (a) by reacting ZrCl4 with aliphatic ethers at elevated temperatures, or (b) by thermally decomposing the addition compounds of ZrCl4 and aliphatic ethers, alkyl chlorides being produced as a by-product.  The preferred form of reaction (a) is to react the aliphatic ether in gas or vapour form with ZrCl4 at 150-300 DEG  C.  The preferred form of reaction (b) takes place at 120-400 DEG  C.; if the temperature is about 150 DEG  C. and the duration of the reaction is long (e.g. 35-90 hours), the products are watersoluble with high values for x and y; if the temperature is about 250 DEG  C., the products are water-insoluble, with low values of x and y.  Pressures may be normal or elevated, higher pressures favouring the production of alkyl chlorides.  In the examples, the ether used is dimethyl ether, so that R is methyl and the alkyl chloride produced is methyl chloride; values of x and y are given.